CN86106818A - Organo-tin compound and contain their agricultural chemicals - Google Patents
Organo-tin compound and contain their agricultural chemicals Download PDFInfo
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- CN86106818A CN86106818A CN86106818.1A CN86106818A CN86106818A CN 86106818 A CN86106818 A CN 86106818A CN 86106818 A CN86106818 A CN 86106818A CN 86106818 A CN86106818 A CN 86106818A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/22—Tin compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
- A01N55/04—Tin
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/22—Tin compounds
- C07F7/2224—Compounds having one or more tin-oxygen linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/22—Tin compounds
- C07F7/226—Compounds with one or more Sn-S linkages
Abstract
The present invention is the asymmetric organo-tin compound of relevant formula (I) expression, its preparation method and contain the agricultural chemicals of formula (I) compound.
R in the formula
1, R
★, X is identical with its definition in specification sheets with m.
Description
More relevant new asymmetric three organic radical tin compounds, their preparation and the formulation of pesticides that contain these new compounds of the present invention.
There are many kinds to colonize in insect on the plant.Wherein acarina (Acarina) to many be a farmer and garden crop can cause huge infringement, thereby aspect Agricultural management, cause serious problem.Because this phytophagous mite class can very fast generation resistance to agricultural chemicals, the therefore effective agricultural chemicals constantly seeking new always.
The useful organic compound of these mite classes of known control comprises, for example, and Cyheratin(trade name Plictran
, United States Patent (USP) 3264177) and fenbutatin oxide(trade name osadan
, United States Patent (USP) 3657451).But these compound known have a shortcoming, and promptly their pesticide activity changes along with the kind of insect, and some existing chemical sproof tetranychid is not suppressed ability.
Consider above-mentioned situation, inventors of the present invention have carried out extensive studies to organo-tin compound, and in the hope of therefrom finding to have the active compound of pesticide activity, particularly those have chemical sproof spider mite kind compounds effective to existing agricultural chemicals.Result of study shows: the asymmetric three organic radical tin compounds of following formula I representative have good pesticide activity, have chemical sproof spider mite kind especially true to those to known organo-tin compound.
The invention provides the asymmetric three organic radical tin compounds of representing by formula I with pesticide activity:
R wherein
1Represent alkyl, cycloalkyl or aralkyl, work as R
1When being alkyl, R
*Represent fluorophenyl or trifluoromethyl; Work as R
1When being cycloalkyl, R
*Represent dichlorophenyl, neo-pentyl, trimethyl silicane methyl, 3,5-dimethylphenyl silicon methyl or following formula
The gene of representative, wherein R
2Represent halogen, trifluoromethyl, or alkoxyl group; Work as R
1When being aralkyl, R
*Represent the 2-thienyl, 3-thienyl, neo-pentyl, trimethyl silicane methyl, 3,5-dimethylphenyl silicon methyl or following formula
The group of representative, wherein R
3, R
4And R
5Represent hydrogen separately, halogen, trifluoromethyl, low alkyl group or alkoxyl group.M represents 1 or 2, and X represents halogen, imidazolyl, and triazolyl, thiophenyl or be selected from a kind of in the following groups:
-OCOR
6，-SSCNR
7R
8，-NCO，-NCS，
，
-SCH
2COOR
6，-SR
7，
When m is 1, R wherein
6Represent alkyl, R
7And R
8Represent low alkyl group separately, R
9And R
10Represent hydrogen or low alkyl group separately; When m was 2, they represented oxygen, sulphur separately, or were selected from a kind of in the following groups:
-OSO
2O-，
Following term used in open explanation of the present invention and claim is just like giving a definition.
Term " alkyl " refers to have the saturated hydrocarbyl of the straight or branched of one to 12 carbon atom, comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl, neo-pentyl, 1-methyl butyl, 1, the 2-dimethylbutyl, hexyl, heptyl, octyl group, nonyl, decyl etc.
Term " low alkyl group " refers to 6 below the carbon atom, defines aforesaid alkyl.
Term " aralkyl " refers to the alkyl that replaced by aryl comprise phenmethyl, styroyl, hydrocinnamyl, methylbenzene methyl, α, alpha-alpha-dimethyl styroyl etc.
Term " cycloalkyl " refers to contain the saturated cyclic alkyls of three to ten carbon atoms, cyclopropyl for example, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl etc.
Term " halogen " refers to chlorine, bromine, iodine and fluorine.
Term " insect " here is interpreted as deleterious insect of plant and mite class, those phytophagous insects particularly, and term " agricultural chemicals " or " formulation of pesticide " comprise sterilant and miticide.
The method for preparing compound shown in the formula I will describe in detail below.
After this (I a), it can prepare by following reaction path I to be called compound in the compound (I) when X is halogen for short; X is the compound (I) of other group except that halogen, can (I a) prepares by following reaction path II to IV by compound.
In the above-mentioned reaction path, R
*And R
1Described as defined above, Hal, y
1And y
2Can be chlorine separately, bromine or iodine; N is 1 or 2, and condition is when n is 1, R
*Be a siliceous group, when n is 2, R
*Be an aryl or neo-pentyl.Below these are reflected at and are described in detail.
The first step
Compound (II) with halogenation organotin (III) reaction, produces the asymmetric four organic radical tin compounds with logical formula IV in a kind of appropriate solvent in 5 ℃ to 100 ℃ temperature ranges.Preferred solvent is an ethers, as ether, and butyl ether, tetrahydrofuran (THF) etc.
Starting compound (II) can make under the condition for preparing Grignard reagent usually easily.
Have the raw material organotin halogenide of logical formula III, when n is 2, can be expressed as
（R
1）
2Sn（y
2）
2
It can be by the corresponding symmetrical four organic radical tin compounds with following formula
（R
1）
4Sn
R wherein
1The same and tin halides of definition is redistributed reaction by alkyl and is made according to known experimental arrangement.Asymmetric phenyl two organic radical tin halides promptly are equivalent to n in the formula and are 1 formula III starting compound, can be expressed as
（R
1）
2Sn（phe）y
2
Itself is a kind of target compound of the present invention, therefore can be by above-mentioned starting compound (III), and wherein n is 2, makes by the reaction path I.
Second step
Halogenating reaction with asymmetric four organic radical tin compounds of logical formula IV, be according to a conventional method by the gas halogen is directly introduced, perhaps halogen is dissolved in to be added in the appropriate solvent again and carries out in the asymmetric four organic radical solution of tin that are dissolved in a kind of solvent, temperature of reaction maintains-50 ℃ to 30 ℃.Appropriate solvent used in the reaction comprises chloroform, tetracol phenixin, benzene, toluene, heptane, hexane etc.Particularly preferred solvent is chloroform and tetracol phenixin.
The preferred mol ratio of asymmetric four organic radical tin compounds (IV) and halogen is about 1: 1.Temperature of reaction preferably maintains between-10 ℃ to 10 ℃.
After halogen or halogen-containing solution added, reaction had also just stopped.Reaction mixture is concentrated, separate desired compound, available if desired recrystallization, vacuum distilling or column chromatography are purified.(I at room temperature is a liquid or solid a) to the asymmetric three organic radical tin halides that make like this.
(I a) can easily be converted into other target compound of the present invention to these halogenide, for example is converted into oxyhydroxide with known experimental arrangement by following reaction path, and is two-(asymmetric three organic radical tin) oxide compound and other various derivatives.
The reaction path II
The reaction path IV
In above-listed each reaction path, R
*, R
1, R
6, R
7, R
8, R
9, R
10The same with the Hal definition, Az represents 1,3-imidazoles-1-base or 1,2,4-triazol-1-yl.Required reaction conditions is known to those skilled in the art, also publishes, and for example Rlnhan is described at Chemical Reviews1960 (October) 459-539 page or leaf.
Formula I compound provided by the invention now illustrates fabulous pesticide activity to each order kind food plant insect, for example to acarina (Aearina), lepidopteran (Lepidoptera), Hemiptera (Hemip tera), Coleoptera (Coleoptera), Orthoptera (Orthoptera) and Diptera (Diptera) etc.More particularly compound (I) has fabulous restraining effect to multiple acarina pest, for example to tangerine Panonychus citri (Panony chus citri), elm (apple) Panonychus citri (Panony chus Ulmi), red spider mite (Tetranyehus Viennensis), may examine prestige tetranychus telarius (Tetranychus Kanzawai), tangerine short hairs mite (Brevipalpus lewisi), priet mite (Brevipalpus obovatus) and tangerine rust mite (Aculops pelekassi) etc.In addition, compound (I) then can not damage crops and garden crop, or only cause small, the injury that is easy to recover.
There are some tetranychid orders for example may examine the prestige tetranychus telarius to known miticide Cyhexatin(trade name Plictran,
Produce by Dow Chemical Company, see United States Patent (USP) 3264177) and fenbutatin oxide(trade name Osadan
, the Shell Oil Co. produce, and see United States Patent (USP) 3657451) and the demonstration resistance.Compound provided by the invention (I), as previously mentioned, even to the existing drug-fast mite class of known section mite agent is also now illustrated fabulous restraining effect.
Therefore, the present invention also provides a kind of formulation of pesticide, and it comprises as the formula I compound of active ingredient and some appropriate carriers and/or co-adjuvant.
Formulation of pesticide of the present invention can have the form of any needs, wettable powder for example, emulsifying concentrated solution, the dust shape thing etc. that maybe can flow.Their method for making is by the conventional method of this specialty, promptly the carrier or the co-adjuvant of compound (I) and one or more non-plant toxicities is mixed.Used carrier and co-adjuvant comprise various liquid such as organic solvent and water, tensio-active agent, also comprise particulate state and finely powdered solid matter etc.
Wettable powder can make by compound (I) and following material are mixed: a kind of solid carrier such as clay, talcum, hard charcoal, diatomite or wilkinite, a kind of ionic or nonionic emulsifier or dispersion agent such as senior alkoxyl group sulfonate, the polyoxyethylene sorbitol acid anhydride, alkyl phenoxy polyethoxyethanols or sulphonated oil.If desired, also can add wetting agent, protection colloid etc.Emulsifying concentrated solution can be dissolved in compound (I) in a kind of suitable organic solvent, makes toward wherein adding a kind of suitable tensio-active agent again.It can be the water concentrated solution that emulsification forms in oil, also can be the oil concentrated solution that emulsification forms in water, and they all have the high density that can compare with concentrated aioli.
Formulation of pesticide of the present invention can use separately, also can with other miticide, sterilant, fungicides, plant-growth regulator, fertilizer etc. mix the back to be used.
The content of compound (I) in formulation of pesticide, generally by 7 to 70 weight percentage, preferred degree of enrichment is 20 to 50 weight percentage in wettable powder or emulsible concentrated solution.Be used for the amount of the formulation of pesticide at position, insect place, depend on many factors, such as administrated method, season, agents area, the kind of insect and crop etc., but the common consumption of formulation of pesticide is 500 to 10000 times of dilutions, preferably dilute 1000 to 5000 times after, per 10 ares of usefulness, 200 to 600 liters.
The dust formulation of pesticide contains compound (I) 0.5 to 10 weight percentage usually, and preferred concentration is 2 to 5 weight percentage, and consumption is per 10 are 3 to 5 kilograms.Contain compound (I) 0.5 to 10 weight percentage in the meticulousr dust formulation of pesticide, preferred concentration 1 to 5 weight percentage, amount of application is per 10 are 1.5 to 5 kilograms.
Following detailed example, prescription and experiment are to be used for illustrating specific embodiments more of the present invention.
Example 1
Fluoridize two α, α-(dimethyl benzene ethyl)-m-trifluoromethylphenyl tin compound 1)
1) two (α, alpha-alpha-dimethyl styroyl)-two (m-trifluoromethylphenyl) tin
On 1000 milliliters of four-necked bottles, install agitator, thermometer, dropping funnel and prolong.Add magnesium (12.5 grams, 0.51 mole) and use air in the nitrogen purge bottle.From 3 milliliters of mixtures of being formed by m-trifluoromethyl phenyl-bromide (113.4 grams, 0.504 mole) and tetrahydrofuran (THF) (220 gram) of the each dropping of dropping funnel.When mixture was heated to 60 to 70 ℃, reaction began to take place under flue gas, and the temperature of at this moment keeping solution is at 60 ℃, and added all solution of m-trifluoromethyl phenyl-bromide in tetrahydrofuran (THF) at about about 2 hours.
Add the back mixture was refluxed 5 hours, then cool to room temperature.Drip dichloride two (α, alpha-alpha-dimethyl styroyl) tin (85.6 grams, 0.188 mole) from separating funnel again about 30 minutes and be dissolved in solution in the tetrahydrofuran (THF) (200 gram), holding temperature is at 10 to 20 ℃ during dropping.Make mixture keep refluxing 7 hours after adding.After mixture is chilled to room temperature, add saturated aqueous ammonium chloride solution hydrolysis.Tell organic phase, wash with water, filter and concentrating under reduced pressure, obtain a brown viscous liquid, decolour toward wherein adding normal hexane (300 gram) and activated clay (50 restrain), after mixture filters again concentrating under reduced pressure obtain 118 gram two (α, alpha-alpha-dimethyl styroyl)-two (m-trifluoromethylphenyl) tin, be colourless limpid thick liquid.Show that with this thick liquid of gas chromatographic analysis its purity is 95%.Tin content 17.2%(theoretical value: 17.6%)
2) fluoridize two (α, the alpha-alpha-dimethyl styroyl)-m-trifluoromethylphenyl tin is being equipped with agitator, thermometer, in 500 milliliters of four-necked bottles of dropping funnel and condenser, adding example 1-(1) two (α that make in, the alpha-alpha-dimethyl styroyl)-two (m-trifluoromethylphenyl) tin (80 gram, 0.118 mole) and chloroform (200 restrain).Under agitation, the temperature of keeping reaction mixture is at-5 ℃ to 0 ℃, in about 2.5 hours, from the mixture of dropping funnel dripping bromine (19 grams, 0.216 grammeatom) and chloroform (100 milliliters).Add the back and allow mixture to be warmed to room temperature, filter, concentrating under reduced pressure gets 72.2 gram bromination two (α, alpha-alpha-dimethyl styroyl)-m-trifluoromethylphenyl tin, is a viscous liquid.The purity of gas chromatographic analysis indication is 93%.With the crude product bromination two (α that make like this, the alpha-alpha-dimethyl styroyl)-and m-trifluoromethylphenyl tin (72.2 gram) and benzene (120 gram), Potassium monofluoride (14 gram), water (56 gram) is placed in 500 milliliters of three-necked bottles together, mixture heating up was refluxed 2 hours, divide to fall water after reaction finishes, organic phase washes with water, filters, concentrating under reduced pressure, the resistates that obtains-20 ℃ by normal hexane in recrystallization, obtain 33.8 grams and fluoridize two (α, alpha-alpha-dimethyl styroyl)-m-trifluoromethylphenyl tin.This material is a liquid in room temperature, refractive index n
30=1.5555.Tin content 21.1%(theoretical value: 21.6%)
Example 2
Bis oxide (two (α, alpha-alpha-dimethyl styroyl)-m-trifluoromethylphenyl tin)
(compound 3)
Two (α, alpha-alpha-dimethyl the styroyl)-m-trifluoromethylphenyl tin (13 grams, 23.7 mmoles) of fluoridizing that obtain by example 1 are dissolved in the benzene (60 gram).In this solution, add 20% aqueous sodium hydroxide solution (7.2 gram), reaction mixture was reacted one hour between 75 ℃ to 80 ℃.Remove water layer after reaction finishes, organic layer washes and filters decompression with water and steams benzene down from organic layer, obtains 11.8 gram bis oxide (two (α, alpha-alpha-dimethyl styroyl))-m-trifluoromethylphenyl tin), be a light yellow viscous liquid.Refractive index: n
30=1.5651; Tin content 21.9%(theoretical value: 22.1%)
Example 3
Acetic acid two (α, alpha-alpha-dimethyl styroyl)-m-trifluoromethylphenyl tin (compound 5)
The bis oxide that makes by example 2 (two (α, alpha-alpha-dimethyl styroyl))-m-trifluoromethylphenyl tin) (6 gram, 5.57 mmoles) be dissolved in the normal hexane (30 gram).Add Glacial acetic acid (0.67 gram, 11.16 mmoles) in this solution, the azeotropic dehydration process takes place therebetween 70 to 75 ℃ of heating 1 hour in reaction mixture.After reaction is finished, mixture being filtered, remove normal hexane by steaming in the filtrate, obtain 6.4 gram acetic acid two (α, alpha-alpha-dimethyl styroyl)-m-trifluoromethylphenyl tin, is a light yellow viscous liquid, refractive index: n
30=1.5465.Tin content: 20.1%(theoretical value: 20.1%).
Example 4
Dimethyl dithiocarbamic acid two (α, alpha-alpha-dimethyl styroyl)-m-trifluoromethyl tin
(compound 6)
The two (α that fluoridize that make by example 1, the alpha-alpha-dimethyl styroyl)-m-trifluoromethylphenyl tin (10 grams, 18.2 mmole) be dissolved in the benzene (50 gram), toward wherein add the solution that Sodium dimethyldithiocarbamate 40min dihydrate (3.9 grams, 21.8 mmoles) forms in water (15.6 gram).Reaction mixture heated 1 hour between 75 ℃ to 80 ℃, removed water layer, and organic layer washes with water and filters.The filtrate decompression distillation is to remove benzene, and the resistates that obtains obtains 11.4 gram dimethyl dithiocarbamic acid two (α, alpha-alpha-dimethyl styroyl)-m-trifluoromethylphenyl tin by the sherwood oil recrystallization, is a white solid.
Fusing point 96-97 ℃.Tin content: 18.1%(theoretical value: 18.2%)
Example 5
Chlorination two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltin (compound 25)
Two (α, alpha-alpha-dimethyl styroyls)-two o-trifluoromethyl phenyltins (113 gram), a kind of flaxen thick liquid is that the guidance system by example 1 gets, but with o-trifluoromethyl phenyl-bromide (113.4 grams, 0.502 mole) replacement m-trifluoromethyl phenyl-bromide.The liquid that obtains is through gas chromatographic analysis, and indication purity is 96.3%.Tin content is the 17.3%(theoretical value: 17.6%)
Two (α, alpha-alpha-dimethyl styroyls)-two o-trifluoromethyl phenyltins (80 grams, 0.108 mole) that make above are dissolved in the chloroform (200 gram), and holding temperature is introduced chlorine (7.6 grams, 0.216 grammeatom) in solution between 0 ℃ to 5 ℃.With the reaction mixture concentrating under reduced pressure, the resistates that obtains obtains 61.1 gram chlorination two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins by recrystallizing methanol, is white solid then.Its purity of gas chromatographic analysis is 97.3%.
Fusing point: 49-50 ℃.Tin content: 21.0%(theoretical value: 21.0%).
Example 6
Bis oxide (two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins) (compound 16)
The chlorination two (α that make in the example 5, the alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltin (13.4 grams, 23.7 mmole) be hydrolyzed by the experimental arrangement described in the example 2, the product that obtains is by the normal hexane recrystallization, provide 12.1 gram bis oxides (two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins)
Fusing point: 42-44 ℃.Tin content: 21.8%(theoretical value: 22.1%).
Example 7
Two (α, alpha-alpha-dimethyl styroyl)-(o-trifluoromethyl phenyl)-(1,2,4 ,-triazol-1-yl) tin (compound 7)
The bis oxide that makes in the example 6 (two (α, the alpha-alpha-dimethyl styroyl)-and the o-trifluoromethyl phenyltin) (6 grams, 5.57 mmole) and 1,2,4-triazole (0.77 gram, 11.1 mmole) be dissolved in the toluene (30 gram), mixture is 110 to 112 ℃ of heating 1 hour, to finish the azeotropic dehydration process.Filter reaction mixture, benzene is removed in distillation, and (two (α, alpha-alpha-dimethyl styroyl) (o-trifluoromethyl phenyl) (1,2, the 4-triazol-1-yl) tin is a kind of light yellow viscous liquid to obtain 6.5 grams.
Refractive index: n
30=1.5690.Tin content: 20.7%(theoretical value: 19.8%).
Example 8
Sulfuric acid two (two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins)
(compound 55)
The bis oxide that in example 6, makes (two (α, the alpha-alpha-dimethyl styroyl)-and the o-trifluoromethyl phenyltin) (2.7 grams, 2.51 mmole) be dissolved in the benzene (30 milliliters), toward wherein adding 50% aqueous sulfuric acid (5 milliliters), stirring at room reaction mixture 15 minutes.Tell and discard water layer, organic layer washes with water, filters, and concentrating under reduced pressure provides 2.8 gram sulfuric acid two (two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins), is light yellow viscous liquid.
Refractive index: n
30=1.5700.Tin content 21.0%.(theoretical value: 20.5%).
Example 9
Fluoridize two (α, alpha-alpha-dimethyl styroyls)-to fluorophenyl tin (compound 9)
Two (α, the alpha-alpha-dimethyl styroyl)-two pair fluorophenyl tin (100.9 gram), be according to embodiment 1-(1) a kind of colourless viscous liquid of making of described method, but replace the m-trifluoromethyl phenyl-bromide in the original experimental arrangement with p-Fluoro bromo benzene (89.3 grams, 0.51 mole).
Gas chromatographic analysis points out that the purity of desired compound is 96.9% in this liquid.Tin content is 20.6%.(theoretical value: 20.6%).
With the two (α that make above, the alpha-alpha-dimethyl styroyl)-two (to fluorophenyl) tin (62.1 grams, 0.108 mole) is dissolved in the chloroform (200 gram), keeps resulting solution temperature at-15 ° to-20 ℃, feed chlorine (7.6 grams, 0.216 grammeatom).Then the reaction mixture concentrating under reduced pressure, provide 56 gram chlorinations two (α, alpha-alpha-dimethyl styroyl)-, be weak yellow liquid to fluorophenyl tin.Gas chromatographic analysis points out that desired degree of purity of production is 87.5%.
Crude product chlorination two (α, alpha-alpha-dimethyl styroyl)-fluorophenyl tin (50 gram) and Potassium monofluoride (5.8 grams, 0.1 mole) are mixed, heating is 2 hours under the condition of benzene (120 gram) and water (23 gram) existence.Remove the water layer in the reaction mixture, organic layer washes with water, filters and concentrating under reduced pressure.The resistates that obtains like this is by the sherwood oil recrystallization, provides 38.5 grams and fluoridizes two (α, alpha-alpha-dimethyl styroyls)-to fluorophenyl tin, be a white solid.
Fusing point: 59-62 ℃.Tin content: 23.2%(theoretical value: 23.8%).
Example 10
Sulfuration two (two (α, alpha-alpha-dimethyl styroyls)-to fluorophenyl tin) (compound 58)
Fluoridize two (α, alpha-alpha-dimethyl styroyls)-fluorophenyl tin (6 gram, 12 mmoles) is dissolved in the benzene (30 milliliters) with what make in the last example.Toward the water that wherein adds potassium sulphide (1 gram, 17.7 mmoles) (4 gram) solution, and mixture backflow 2 hours.
By after telling in the mixture and removing water layer, organic layer washes with water, filters.Decompression down steams benzene, obtains 6.4 gram sulfurations pair (two (α, alpha-alpha-dimethyl styroyls)-to fluorophenyl tin), is light yellow viscous liquid.
Refractive index: n
30=1.6155, tin content: 23.1%(theoretical value: 23.9%).
Example 11
Bis oxide (two (α, alpha-alpha-dimethyl styroyls)-to fluorophenyl tin) (compound 17)
With the two (α that fluoridize that make in the example 9, the alpha-alpha-dimethyl styroyl)-to fluorophenyl tin (15 grams, 30 mmoles) and 20% aqueous sodium hydroxide solution (9 gram), press example 2 described experimental arrangements, can make bis oxide (two (α, the alpha-alpha-dimethyl styroyl)-to fluorophenyl tin), be a white solid.
Fusing point: 84-86 ℃.Tin content: 24.5%.(theoretical value: 24.3).
Example 12
Two (α, alpha-alpha-dimethyl styroyl)-(to fluorophenyls) (1,3-imidazoles-1-yl) tin (compound 54)
The bis oxide that makes in the example 11 (two (α, the alpha-alpha-dimethyl styroyl)-to fluorophenyl tin) (6 grams, 6.14 mmole) and 1,3-imidazoles (0.83 gram, 12.3 mmole) be dissolved in the toluene (30 gram), with mixture 110-112 ℃ of heating 1 hour, to finish the virtue dehydration of boiling.Reaction mixture is filtered, boil off benzene, provide a solid residue, it by recrystallization in the normal hexane, is promptly produced 5.1 2 (α, alpha-alpha-dimethyl styroyl)-(to fluorophenyls) (1,3-imidazoles-1-yl) tin.
Fusing point 123-127 ℃.Tin content: 21.2%.(theoretical value: 21.7%).
Example 13
Fluoridize dicyclohexyl-to fluorophenyl tin (compound 14)
Dicyclohexyl-two pair fluorophenyl tin (85.2 gram) is according to embodiment 1(1) described in experimental arrangement make, but with p-Fluoro bromo benzene (89.3 grams, 0.51 mole) and dichloride dicyclohexyl tin (76.9 grams, 0.216 m-trifluoromethyl phenyl-bromide and dichloride two (α, the alpha-alpha-dimethyl styroyl) tin in the original experimental arrangement of replacement mole).By the gas chromatographic analysis of the reaction product of recrystallization in the Virahol, indication purity is 98.6%.
Fusing point: 88-90 ℃.Tin content: 25.1%.(theoretical value: 25.0%)
With example 1(2) described experimental arrangement is identical, above-mentioned product (20 grams, 0.042 mole) earlier and bromine reaction produce crude product bromination dicyclohexyl-to fluorophenyl tin, and then handle with Sodium Fluoride and promptly to produce 11.7 and restrain and fluoridize dicyclohexyl-, be a white solid fluorophenyl tin.
Fusing point: 234-240 ℃ (decomposition).Tin content: 29.9%.(theoretical value: 29.1%).
Example 14
Isocyanic acid two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltin (compound 60)
The chlorination two (α that make in the example 5, the alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltin (6 grams, 10.6 mmole) and Zassol (1.1 gram, 15.9 mmoles), acetone (40 gram) be placed on together in the flask, mixture was refluxed 3 hours.Toward wherein adding benzene (50 gram) and water (30 gram).Remove water, organic layer washes with water and filters.
Pressure reducing and steaming benzene provides 5.6 gram isocyanic acid two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins, is colourless viscous liquid.
Refractive index: n
30=1.5609.Tin content: 21.0%(theoretical value: 20.7%).
Example 15
Isothiocyanic acid two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltin (compound 59)
The chlorination two that makes in the example 5 (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltin (6 grams, 10.6 mmoles), and potassium sulfocyanate (1.5 grams, 15.9 mmoles), benzene (40 gram), water (10 gram) is placed in the flask together, and mixture heating up was refluxed 2 hours.Remove water, organic phase washes filtration with water, and pressure reducing and steaming benzene obtains 6.0 gram isothiocyanic acid two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins, is colourless viscous liquid.
Refractive index: n
30=1.5787.Tin content: 20.5%(theoretical value: 20.2%)
Example 16
Methyl sulfuration two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins (compound 67)
The chlorination two that makes in the example 5 (α, alpha-alpha-dimethyl ethyl)-o-trifluoromethyl phenyltin (6 grams, 10.6 mmoles), with 15% methyl sodium sulfide solution (7.4 grams, 15.9 mmole), benzene (40 gram) is placed in the flask together, and mixture heating up was refluxed 2 hours.Shift out water layer, organic layer washes with water and filters.Pressure reducing and steaming benzene obtains 4.6 gram methyl sulfurations, two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins, is colourless viscous liquid.
Refractive index: n
30=1.5804.Tin content: 20.9%(theoretical value: 20.6%).
Example 17
Benzene oxidation two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltin (compound 68)
The bis oxide that makes in the example 6 (two (α, the alpha-alpha-dimethyl styroyl)-and the o-trifluoromethyl phenyltin) (6 grams, 5.6 mmole) and phenol (1.0 the gram, 11.2 mmole), toluene (40 gram) is placed in the flask together, and mixture is gone up substantially according to the experimental arrangement described in the example 7 and reacted.A residue that obtains promptly produces 4.4 gram benzene oxidations, two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins by the sherwood oil recrystallization after boiling off toluene, is white solid.
Fusing point: 69-71 ℃.Tin content: 19.1%(theoretical value: 19.0%)
Example 18
Benzene sulfuration two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins (compound 69)
The bis oxide that makes in the example 6 (two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins) (6.0 grams, 5.6 mmoles), and thiophenol (1.2 grams, 11.2 mmole), toluene (40 gram) is put together, presses the experimental arrangement described in the embodiment 7 and handles.Product obtains 5.2 gram benzene sulfurations, two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins by the normal hexane recrystallization, is white solid.
Fusing point 81-82 ℃.Tin content: 18.7%.(theoretical value: 18.6%)
Example 19
0,0-diethyldithiophosphoric acid S-two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltin (compound 71)
Basic identical with the experimental arrangement described in the example 7, the bis oxide that makes according to example 6 (two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltins) (6.8 grams, 6.4 mmoles), with 0,0-diethyl dithiophosphate (2.2 grams, 12.8 mmoles), toluene (40 gram) one reacts, promptly obtain 8.0 grams 0,0-diethyldithiophosphoric acid S-two (α, alpha-alpha-dimethyl styroyl)-o-trifluoromethyl phenyltin is colourless viscous liquid.
Refractive index: n
30=1.5759.
Example 20
Bromination two (α, alpha-alpha-dimethyl styroyl)-(4-chloro-3-trifluoromethyl) tin (compound 74)
Two (α, the alpha-alpha-dimethyl styroyl)-two (4-chloro-3-trifluoromethyl) tin (125.8 gram), a kind of light yellow viscous liquid, according to example 1-(1) described in essentially identical experimental arrangement make, but replace the m-trifluoromethyl phenyl-bromide in the original experimental arrangement with 4-chloro-3-methyl bromobenzene trifluoride (131.0 grams, 0.504 mole).The purity of gas chromatographic analysis indication gained product liquid is 98.5%.Tin content 15.6%.(theoretical value 15.9%)
Then according to example 1-(2) described in, two (α, alpha-alpha-dimethyl styroyls)-two (4-chloro-3-trifluoromethyl) tin that makes above (87.8 grams, 0.118 mole) and bromine reaction, obtain a faint yellow solid (79.2 gram).This solid is heavy total brilliant with methyl alcohol (200 gram), obtain 65.7 gram bromination two (α, alpha-alpha-dimethyl styroyl)-4-chloro-3-trifluoromethyl tin, be white solid.Its purity of gas chromatographic analysis indication is 99.0%.Fusing point 72-74 ℃.Tin content: 18.3%.(theoretical value: 18.4%)
Example 21
Fluoridize two (α, alpha-alpha-dimethyl styroyl)-2,4 difluorobenzene base tin (compound 79)
Two (α, the alpha-alpha-dimethyl styroyl)-two (2, the 4-difluorophenyl) tin (107.9 gram), a kind of colourless viscous liquid, be according to example 1-(1) described in experimental arrangement make, but with 2,4-difluoro bromobenzene (98.4 grams, 0.51 mole) replaces the m-trifluoromethyl phenyl-bromide in the original experimental arrangement.The purity of gas chromatographic analysis indication gained liquid is 95.5%.Tin content 19.0%.(theoretical value: 19.4%)
Then according to example 1-(2) described in, product that makes above (72.1 grams, 0.118 mole) and bromine reaction, promptly obtain crude product bromination two (α, the alpha-alpha-dimethyl styroyl)-2,4-difluorophenyl tin, it is handled with Sodium Fluoride again, and the product that obtains is by the normal hexane recrystallization, promptly provide 30.6 grams and fluoridize two (α, the alpha-alpha-dimethyl styroyl)-and 2,4 difluorobenzene base tin, be white solid.
Fusing point: 60-65 ℃.Tin content: 22.6%(theoretical value: 22.9%)
Example 22
Chlorination two (α, alpha-alpha-dimethyl styroyl)-2,4,5-trifluorophenyl tin (compound 92)
Two (α, the alpha-alpha-dimethyl styroyl)-two (2,4, the 5-trifluorophenyl) tin (113.1 gram), a kind of light yellow viscous liquid is according to making with essentially identical experimental arrangement described in the example 1, but with 2,4,5-trifluorobromobenzene (105.9 grams, 0.502 mole) replaces the m-trifluoromethyl phenyl-bromide in the original experimental arrangement.Gas chromatographic analysis points out that the purity of gained liquid is 96.0%.Tin content 17.8%.(theoretical value: 18.3%)
Then above-mentioned reaction product (76.4 grams, 0.118 mole) and the chlorine reaction, and by above-mentioned reaction mixture being carried out aftertreatment with essentially identical experimental arrangement described in the embodiment 5, product is by recrystallization in the normal hexane, provide 39.3 gram chlorinations two (α, alpha-alpha-dimethyl styroyl)-2,4,5-trifluorophenyl tin is white solid.Gas chromatographic analysis points out that this solid purity is 99.9%.
Fusing point: 65-67 ℃.Tin content: 21.7%.(theoretical value: 21.5%)
Example 23
Fluoridize two (α, alpha-alpha-dimethyl styroyl)-rubigan tin (compound 108)
Two (α, the alpha-alpha-dimethyl styroyl)-two (rubigan) tin, (107.5 gram) a kind of colourless viscous liquid, according to preparing with example 1 described essentially identical experimental arrangement, but replace the m-trifluoromethyl phenyl-bromide in the original experimental arrangement with para chlorobromobenzene (97.4 grams, 0.51 mole).The purity that gets liquid that gas chromatographic analysis is pointed out is 97.5%.Tin content 19.1%.(theoretical value 19.5)
With example 1-(2) described in the experimental arrangement basically identical, with above-mentioned product (71.8 grams, 0.118 mole) and bromine reaction, promptly obtain crude product bromination two (α, the alpha-alpha-dimethyl styroyl)-and rubigan tin, again it and Sodium Fluoride are reacted, the product that obtains is by recrystallization in the normal hexane, 32.7 grams to fluoridize two (α, alpha-alpha-dimethyl styroyl)-rubigan tin be white solid.
Fusing point 104-105 ℃.Tin content: 23.0%(theoretical value: 23.0%)
Example 24
Fluoridize two (α, alpha-alpha-dimethyl styroyl)-phenyltins (compound 144)
Two (α, the alpha-alpha-dimethyl styroyl)-tin diphenyl (108.9), a kind of colourless viscous liquid, according to example 1-(1) described in essentially identical experimental arrangement make, but replace the m-trifluoromethyl phenyl-bromide in the original experimental arrangement with bromobenzene (78.8 grams, 0.502 mole).It is 97.8% that the purity of this liquid is indicated in gas chromatographic analysis.Tin content 21.7%.(theoretical value: 22.0%)
According to example 1-(2) described, can make and fluoridize two (α, alpha-alpha-dimethyl styroyl)-phenyltins with above-mentioned product (80 grams, 0.128 mole), be white solid.
Fusing point: 37-49 ℃.Tin content: 24.9%(theoretical value: 24.7%).
Example 25
Chlorination two (α, alpha-alpha-dimethyl styroyl)-o-methoxyphenyl tin (compound 133)
Two (α, the alpha-alpha-dimethyl styroyl)-two (o-methoxyphenyl) tin (105.9 gram), a kind of colourless viscous liquid, according to example 1-(1) described in essentially identical experimental arrangement make, but replace the m-trifluoromethyl phenyl-bromide in the original experimental arrangement with O-methoxy bromobenzene (93.8 grams, 0.502 mole).Gas chromatographic analysis points out that the purity of this liquid is 96.5%.Tin content 19.5%.(theoretical value: 19%)
With above-mentioned product (70.7 grams, 0.118 mole), according to method described in the embodiment 5 and chlorine reaction, promptly make chlorination two (α, alpha-alpha-dimethyl styroyl-o-methoxyphenyl tin (30.1 gram) is a white solid, and gas chromatographic analysis points out that its purity is 99.5%.
Fusing point: 69-72 ℃.Tin content: 22.7%.(theoretical value: 22.5%).
Example 26
Fluoridize two (α, alpha-alpha-dimethyl styroyl)-3-thienyl tin (compound 215) 1) two (α, alpha-alpha-dimethyl styroyl)-two (3-thienyl) tin
On 1,000 milliliter of four-necked bottle, install agitator, thermometer, dropping funnel and prolong are put into 3 bromo thiophene (75 grams, 0.0461 mole) and anhydrous diethyl ether (200 gram).The temperature of keeping reaction mixture drips n-Butyl Lithium (185.3 gram) (15% hexane solution) below-50 ℃ from dropping funnel.Maintain after adding below-50 ℃ and stirred 10 minutes, in about 30 minutes, holding temperature drips dichloride two (α at-50 to-60 ℃ from dropping funnel then, the alpha-alpha-dimethyl styroyl) tin (73.5 grams, 0.161 mole) tetrahydrofuran (THF) (140 gram) solution.After adding, mixture stirred 2 hours under same temperature, allowed it slowly to be warming to room temperature, and restir 1 hour.Add entry (120 milliliters) then with the reaction mixture hydrolysis.Tell organic layer, add hexane (200 gram), wash with water, filter, concentrating under reduced pressure gets a brown viscous liquid.In this liquid, add E hexane (300 gram) and activated clay (50 gram) decolouring, filtering mixt, concentrating under reduced pressure gets 81.7 grams, two (α, alpha-alpha-dimethyl styroyl)-two (3-thienyl) tin, is a water white transparency thick liquid.Gas chromatographic analysis points out that the purity of this liquid is 95.0%.Tin content 21.0%.(theoretical value: 21.6%).
2) fluoridize two (α, alpha-alpha-dimethyl styroyl)-3-thienyl tin
With embodiment 1-(2) described in the experimental arrangement basically identical, the two (α that obtain above, the alpha-alpha-dimethyl styroyl)-two (3-thienyl) tin (80 grams, 0.145 mole) and bromine reaction promptly obtain crude product bromination two (α, the alpha-alpha-dimethyl styroyl)-3-thienyl tin, it and Sodium Fluoride are reacted, and the product that obtains is got 21.5 grams and is fluoridized two (α by recrystallization in the E hexane, the alpha-alpha-dimethyl styroyl)-and 3-thienyl tin, be a white solid.
Fusing point: 85 to 90 ℃.Tin content: 24.7%.(theoretical value: 24.4%)
Example 27
Chlorination dicyclohexyl-p-trifluoromethyl phenyl tin (compound 164)
Crude product dicyclohexyl-two (p-trifluoromethyl phenyl) tin (101.7 gram), a kind of white solid, be according to example 1-(1) experimental arrangement of described basically identical makes, but use methyl bromobenzene trifluoride (113.4 grams, 0.504 mole) and dichloride dicyclohexyl tin (66.9 grams, 0.188 m-trifluoromethyl phenyl-bromide and dichloride two (α, the alpha-alpha-dimethyl styroyl) tin in the original experimental arrangement of replacement mole).Gas chromatographic analysis points out that this solid purity is 93.3%.
With basic identical described in the example 5, above-mentioned product (60 grams, 0.105 mole) and chlorine reaction, again the reaction mixture that obtains is carried out aftertreatment, get 31.5 gram chlorination dicyclohexyl-p-trifluoromethyl phenyl tin, be a white solid.Gas chromatographic analysis points out that this solid purity is 99.0%.
Fusing point: 74-75 ℃.Tin content: 25.8%.(theoretical value: 25.5%)
Example 28
Bis oxide (dicyclohexyl-p-trifluoromethyl phenyl tin) (compound 165)
Chlorination dicyclohexyl-p-trifluoromethyl phenyl the tin that makes in the example 27 (15.0 grams, 32.2 mmoles) being pressed example 6 described methods handle, promptly obtain 11.3 gram bis oxides (dicyclohexyl-p-trifluoromethyl phenyl tin), is a white solid.
Fusing point: 86-89 ℃.Tin content: 26.8%.(theoretical value: 27.1%)
Example 29
Positive fourth oxygen carbonyl methyl sulfuration dicyclohexyl-p-trifluoromethyl phenyl tin (compound 167)
The bis oxide that makes among the embodiment 28 (dicyclohexyl-p-trifluoromethyl phenyl tin) (6.0 grams, 16.8 mmole) and the positive butyl ester of Thiovanic acid (2.0 the gram, 13.6 millimole) be dissolved in together in the toluene (30 gram), mixture carried out azeotropic dehydration in 1 hour 110-112 ℃ of heating, pressure reducing and steaming toluene gets 7.8 gram weak yellow liquids.
Refractive index: n
30=1.5337, tin content: 20.4%.(theoretical value: 20.6%)
Example 30
Fluoridize dicyclohexyl-3,4-dichlorophenyl tin (compound 190)
Dicyclohexyl-two (3, the 4-dichlorophenyl) tin (101.9 gram), a kind of colourless viscous liquid, be according to embodiment 1-(1) described in the experimental arrangement preparation of basically identical, but with 3, (66.9 restrain for 4-dichloro-bromobenzene (113.8 grams, 0.504 mole) and dichloride dicyclohexyl tin, 0.188 m-trifluoromethyl phenyl-bromide and dichloride two (α, the alpha-alpha-dimethyl styroyl) tin in the original experimental arrangement of replacement mole).Gas chromatographic analysis points out that the purity of this liquid is 95.9%.Tin content: 20.2%.(theoretical value: 20.6%).
With the dicyclohexyl-two (3 that makes above, the 4-dichlorophenyl) tin (86.5 gram, 0.150 mole) is by embodiment 1-(2) described method reacts and the reaction mixture that obtains handled, and promptly get 35.5 and restrain and fluoridize dicyclohexyl-3,4-dichlorophenyl tin is a white solid.
193 ℃ of fusing points.Tin content: 26.0%(theoretical value 26.4%)
Embodiment 31
Chlorination dicyclohexyl-trimethyl silicane methyl tin (compound 232)
1) chlorination dicyclohexyl-phenyltin
Dicyclohexyl-tin diphenyl (155.2 gram), a kind of white solid, be according to embodiment 1-(1) described in the experimental arrangement preparation of basically identical, but with bromobenzene (156.2 grams, 1.008 mole) and dichloride dicyclohexyl tin (133.8 grams, 0.376 m-trifluoromethyl phenyl-bromide and dichloride (α, the alpha-alpha-dimethyl styroyl) tin in the original experimental arrangement of replacement mole).Gas chromatographic analysis points out that this solid purity is 94.9%.
With above-mentioned product (150.8 grams, 0.343 mole) react according to method and the chlorine described in the embodiment 5, and the reaction mixture of gained is carried out aftertreatment, product is by recrystallization in the E hexane, obtaining 86.0 gram chlorination dicyclohexyl-phenyltins, is a white solid.Gas chromatographic analysis points out that this solid purity is 98.8%.
Fusing point: 50-52 ℃.Tin content: 30.2%.(theoretical value: 29.9%)
2) chlorination dicyclohexyl-trimethyl silicane methyl tin
Dicyclohexyl-phenyl-trimethyl silicane methyl tin (79.4 gram), a kind of colourless viscous liquid is according to embodiment 1(1) described in the method preparation.But with the chlorination dicyclohexyl-phenyltin that makes above (74.7 grams, 0.188 mole) and trimethyl silicane methyl chloride (30.8 grams, 0.251 dichloride two (α, α dimethyl benzene ethyl) tin and the m-trifluoromethyl phenyl-bromide in the original experimental arrangement of replacement mol).In this example, with 6.1 gram (0.251 mole) magnesium and 110 gram tetrahydrofuran (THF)s.Gas chromatographic analysis points out that the purity liquid of gained is 97.5%
According to the method described in the embodiment 5, above-mentioned product (48.5 grams, 0.108 mole) and chlorine are reacted, and the reaction mixture that obtains is concentrated.Residue gets 35.2 gram chlorination dicyclohexyl-trimethyl silicane methyl tin by recrystallization in the E hexane, is a white solid.Gas chromatographic analysis points out that this solid purity is 99.0%.
74 ℃ of fusing points
Embodiment 32
Bis oxide (dicyclohexyl-trimethyl silicane methyl tin) (compound 233)
According to the method described in the embodiment 2, the chlorination dicyclohexyl that makes among the embodiment 32-trimethyl silicane methyl tin is reacted, and the reaction mixture that obtains carried out aftertreatment, promptly obtain 21.2 gram bis oxides (dicyclohexyl-trimethyl silicane methyl tin), be a white solid, fusing point 151-153 ℃
Embodiment 33
O, O-dibutylphosphoric acid-O-(dicyclohexyl-trimethyl silicane methyl tin) (compound 237)
Press the method described in the embodiment 7, with bis oxide (dicyclohexyl-trimethyl silicane methyl tin) (6.8 grams, 8.9 mmole) and 0,0-dibutylphosphoric acid salt (3.7 grams, 17.8 mmoles), toluene (40 gram) reacts together, by boiling off toluene in the reaction mixture, residue promptly obtains 8.3 gram O by recrystallization in methyl alcohol/acetonitrile, O-dibutylphosphoric acid O-(dicyclohexyl-trimethyl silicane methyl tin), be a white solid.Fusing point: 130-132 ℃.
With with the method for the experimental arrangement basically identical described in top each embodiment, the present invention has also prepared many organo-tin compounds with logical formula I.The physicochemical property of these compounds are listed in the table 1.
Abbreviation below in table 1, having used:
Me: methyl
Et: ethyl
Bu: butyl
Oct: octyl group
Phe: phenyl
Ac: ethanoyl
Tin content representation theory value in the bracket.
Provide below and use all cpds preparation wettable powder of the present invention, emulsifying concentrated solution, the prescription of fine powder etc.
1 wettable powder of filling a prescription
Ingredients by weight is formed
No. 28 compounds 50.0
Clay 40.5
White carbon 5.0
Polyoxyalkylene alkyl allyl ethers sulfuric ester 3.0
Benzene sulfonamide acid esters 1.5
2 emulsifying concentrated solutions of filling a prescription
Ingredients by weight is formed
No. 25 compounds 25.0
Alkyl allyl sulphonic acid ester 3.0
Polyoxyalkylene alkyl allyl ethers 10.0
Dimethylbenzene 42.0
Dimethyl formamide 20.0
No. 25 compounds, alkyl allyl sulphonic acid ester and polyoxyalkylene alkyl allyl ethers are dissolved in dimethylbenzene and the dimethyl formamide equably, promptly get emulsible concentrated solution.Dilute with water in use.
3 fine powders of filling a prescription
No. 33 compounds 15.0
White carbon 20.0
Mazidox isopropyl propionate 0.3
Fine clay 64.7
Above batch mixes is ground.Mixture is worn into very thin powder with the ejection-type masher.Preparation can directly use.
4 powder of filling a prescription
No. 49 compounds 5.0
Clay 91.7
White carbon 3.0
Yatall MA 0.3
With above batch mixes grind powder formulation.Preparation can directly use.
Experiment 1
Sample
Compound dissolution among the available the present invention that experimentizes in few DMF that tries one's best, is added then and contains polysorbas20, and concentration is the distilled water of 100ppm, to make a series of samples of being wanted concentration.
Experimental procedure
A. the inhibition of prodenia litura (Spodoptera Litura) larva
(5 * 5cm) Caulis et Folium Brassicae capitatae leaves immerse in the sample liquid that as above makes, and at air drying.Get two leaves and put into the Petri dish of 9 centimetres of diameters, put into simultaneously the Spodoptera litura larvae in 10 the 3rd length of times in the ware.Control ware temperature is determined the mortality ratio of larva at 25 ℃ after 48 hours.
C. the preparation of small cabbage moth (Plutella Xylostella) larva
7 * 7cm Caulis et Folium Brassicae capitatae leaf is immersed in the sample solution, and at air drying.This leaf is put into the Petri dish of 9 cm diameters, put into the diamondback moth larvae in 10 the 3rd length of times simultaneously in the ware.Control ware temperature is determined the mortality ratio of larva at 25 ℃ after 48 hours.
D.Adoxophyes.SP. the inhibition of larva
The tealeaves of full wafer is immersed in the sample liquid, and at air drying.Get three leaves and put into the polyethylene Petri dish of 6 centimetres of diameters, dark 4cm, put into the Adoxophyes in 10 the 4th length of times simultaneously.SP. larva.Control ware temperature is determined the mortality ratio of larva at 25 ℃ after 48 hours.
The inhibition of caudal lobe cicada E. (Nephotettix Cincticeps) (responsive)
Is seedling age that 6 or 7 rice seedlings of 1.5 to 2 blades are tied, and root is wrapped with sponge.This seedling is put into the polyethylene cup of 6 centimetres dark 4 centimetres of diameters, then cup is put into the rotation spray column, 2 ml sample solution are sprayed on the blade and leaf sheath of seedling, at air drying by it.The seedling of handling covers with transparent plastics garden tube, puts into 10 female larvas simultaneously in the tube of garden.Keep the interior temperature of garden tube at 25 ℃, determine mortality ratio after 48 hours.
The inhibition of I and J black peach aphid (Myzus Persicae) larva (I: responsive J: have drug-fast)
Be full of the polyethylene cup of 6 centimetres dark 4 centimetres of diameters with 0.3% agaropectin, the Chinese Caulis et Folium Brassicae capitatae leaf of 3 * 3 centimetres of a slices is placed on the glue, then an aptery adult of black peach aphid is placed on the Caulis et Folium Brassicae capitatae leaf, let alone to lay eggs, keep surrounding environment at 25 ℃, 24 hours, remove adult, with the rotation spray column 2 ml sample liquid are sprayed on the blade.Experimental system 25 ℃ of insulations 48 hours, is determined to bear the mortality ratio of larva.
M. the inhibition of carmine spider mite (Tetranychus cinnabrinus)
Be full of the polyethylene cup of 6 centimetres dark 4 centimetres of diameters with 0.3% agaropectin, a kind of wild Soybean Leaves of 2 centimetres of a slice diameters is placed on the glue, about 12 carmine spider mite are placed on the blade, kept 24 hours at 25 ℃, remove dead and weak adult, with the rotation spray column 2 ml sample liquid are sprayed on blade and the adult, after this handles, experimental system are maintained 25 ℃, determine mortality ratio after 48 hours.
O. general inhibition of crossing tetranychus telarius (Tetvanychusurticae)
Above-mentioned experimental procedure heavily covered be applied to ordinary maple leaf mite
X. the inhibition of carmine spider mite larva
Be full of the polyethylene cup of 6 centimetres dark 4 centimetres of diameters with 0.3% agaropectin, a kind of wild Soybean Leaves of 2 centimetres of a slice diameters is placed on the glue, 7 carmine spider mite adults are placed on the blade, let alone to lay eggs.Keep 25 ℃ of surrounding environment, 24 hours, remove adult, with the rotation spray column with 2 ml sample spray solutions on blade, experimental system remain on 25 ℃ 7 days, determine to bear the mortality ratio of larva.
Y. the inhibition of ordinary maple leaf mite larva
Above-mentioned experimental procedure heavily covered be applied to the ordinary maple leaf mite larva.
N. the inhibition of carmine spider mite ovum
P. the inhibition of ordinary maple leaf mite ovum
The experimental procedure that X and Y describe is heavily covered the ovum that is applied to carmine spider mite and ordinary maple leaf mite, experimental system remain on 25 ℃ 7 days, by looking into the number of the ovum that number do not hatch, determine the mortality ratio of ovum.
The inhibition of T.Henosepilachna Vigintioctopunctata adult
6 * 6 centimetres of Japanese eggplant leaves are immersed in the sample solution, at air drying, blade is put into 9 cm diameter Petri dishs, in ware, put into 5 Henosepilachna Vigintioctopunctata adults simultaneously, the ware temperature control at 25 ℃, is determined mortality ratio after 48 hours.
R. the inhibition of periplaneta americana (Periplaneta americana) larva
The filter paper that soaks into sample liquid is put into the Petri dish of 9 centimetres of diameters, then 5 periplaneta americana larvas that hatch in back 7 days are put into ware.The ware temperature is maintained 25 ℃, determine mortality ratio after 48 hours.
W. the inhibition of Callosobruchus chinensis (Callosobrucbus Chinensis)
10 of Callosobruchus chinensises that hatch within back 24 hours are put into 1.8 centimetres of diameters, and high 5 centimetres, upper and lower opening has in the spiral garden tube of stainless steel guiding principle, then the garden tube is immersed in the sample liquid, with being immersed in adult in the solution,, determine mortality ratio after 48 hours at 25 ℃ at air drying.
K. the inhibition of the full melon mite of tangerine (Panonychus citri)
Except replace above-mentioned a kind of wild Soybean Leaves with Lemon Leaf, the experimental procedure that is same as M and O heavily covered be applied to the full melon mite of tangerine.
Q. may examine the inhibition (Tetranychus Kanzawai) (drug-fast adult is arranged) of prestige mite
The experimental procedure that is same as M and O heavily covered be applied to drug-fastly may examine prestige mite adult.
Experimental result
Below table 2 show the mortality ratio (%) of the various insects in the indication compound (I) that is exposed to various concentration.Therein various insects are used following symbol.
A. prodenia litura (larva)
C. small cabbage moth (larva)
The D.Adoxophyessp(larva)
E. caudal lobe cicada in (responsive larva)
I. black peach aphid (responsive larva)
J. black peach aphid (resistance larva)
K. the full melon mite of tangerine (adult)
L. the full melon mite of tangerine (ovum)
M. carmine spider mite (adult)
N. carmine spider mite (ovum)
O. ordinary maple leaf mite (adult)
P. ordinary maple leaf mite (ovum)
Q. may examine prestige mite (anti-medicine adult)
R. periplaneta americana (larva)
Henosepila????chna
T.
The Vigintioctopunctata(adult)
W. Callosobruchus chinensis (adult)
X. carmine spider mite (ovum-larva)
Y. ordinary maple leaf mite (ovum-larva)
Table 2 has also been listed with commercially available OSadan
RAnd plictran
RExperimental result in contrast.
Available is to OSadan in experiment Q
RAnd Plictran
RHave that drug-fast may to examine the prestige mite be Yaguchihara from Japan, OKadahara, Shizuoka (Sbizuoka) collects
The experimental result that can be got adult by Yaguchihara and OKadahara is listed in the left side and the right of showing under the 2Q item respectively.
CPCH????866488
Errata
Errata
Claims (3)
1, a kind of compound with logical formula I:
R wherein
1Represent alkyl, cycloalkyl or aralkyl, work as R
1When being alkyl, R
*Represent fluorophenyl or trifluoromethyl; Work as R
1R when being cycloalkyl
*Represent dichlorophenyl, neo-pentyl, the trimethyl silicane methyl, the group of 3,5-dimethylphenyl silicon methyl or following formula representative,
R wherein
2Represent halogen, trifluoromethyl, or alkoxyl group; Work as R
1When being aralkyl, R
*Represent the 2-thienyl, the 3-thienyl, neo-pentyl, the trimethyl silicane methyl, the group of 3,5-dimethylphenyl silicon methyl or following formula representative,
R wherein
3, R
4And R
5Represent hydrogen separately, halogen, trifluoromethyl, low alkyl group or alkoxyl group.M represents 1 or 2, and X represents halogen, imidazolyl, and triazolyl, thiophenyl or be selected from a kind of in the following groups:
-OCOR
6，-SSCNR
7R
8，-NCO，-NCS，
-SCH
2COOR
6，-SR
7，
When m is 1, R wherein
6Represent alkyl, R
7And R
8Represent low alkyl group separately, R
9And R
10Represent hydrogen or low alkyl group separately; When m was 2, they represented oxygen separately, sulphur or be selected from a kind of in the following groups:
2, a kind ofly prepare said method in the claim 1 with logical formula I compound, comprising
A) will have the compound of following formula
R
* 2-Sn(R
1)
2(II a) or R
*Sn(phe) (R
1)
2(II b) (R wherein
*And R
1Definition the same) and halogen reaction, form compound with following formula
B) said compound (III) is provided the compound with formula IV or formula (V) structure with basic hydrolysis:
C) with said compound (III) and Sodium Sulphide reacting metal salt, provide the have formula compound of (V),
D) with said compound (III) with have the compound reaction of following formula,
Wherein M is a kind of basic metal, R
7And R
8Definition the same, provide compound with following formula,
E) with said compound (III) with have the compound reaction of following formula,
MX′CN
Wherein X ' is oxygen or sulphur, and the definition of M is the same, provides the compound with following formula,
F) with said compound (III) with have the compound reaction of following formula,
R wherein
7The same with the definition of M, provide compound with following formula,
G) with said compound (IV) and the reaction of a kind of aliphatic carboxylic acid, provide compound with following formula,
H) with a kind of reaction in said compound (IV) and imidazoles or the triazole, provide compound with following formula,
I) with said compound (IV) with have a kind of phenol reaction of following formula:
R wherein
9And R
10Definition the same, provide compound with following formula,
J) with said compound (IV) and thiophenol reaction, provide compound with following formula,
K) with said compound (IV) with have the compound reaction of following formula,
Wherein X ' and R
7Definition is the same, provides the compound with following formula,
L) with said compound (IV) with have the compound reaction of following formula,
R wherein
6Definition the same, provide compound with following formula,
M) with said compound (IV) with have the compound reaction of following formula,
Provide compound with following formula,
Or
N) with said compound (IV) and sulfuric acid reaction, provide compound with following formula.
3, a kind of formulation of pesticide, it comprises in the claim 1 defined, the compound with logical formula I is as major ingredient, and a kind of appropriate carriers or co-adjuvant.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP195355/1985 | 1985-09-03 | ||
| JP195355/85 | 1985-09-03 | ||
| JP19535585 | 1985-09-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86106818A true CN86106818A (en) | 1987-05-13 |
| CN1016132B CN1016132B (en) | 1992-04-08 |
Family
ID=16339790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86106818A Expired CN1016132B (en) | 1985-09-03 | 1986-09-03 | Pesticide containing organic tin compound |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US4774235A (en) |
| EP (1) | EP0214842B1 (en) |
| JP (1) | JPS62149689A (en) |
| KR (1) | KR920002887B1 (en) |
| CN (1) | CN1016132B (en) |
| AR (1) | AR243195A1 (en) |
| BR (1) | BR8604209A (en) |
| CA (1) | CA1283417C (en) |
| DE (1) | DE3683815D1 (en) |
| ES (1) | ES2001413A6 (en) |
| GB (1) | GB2179943B (en) |
| ZA (1) | ZA866451B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804035A (en) * | 2015-04-15 | 2015-07-29 | 衡阳师范学院 | Tricyclohexanyl-tin 2,7-naphthyl dioxy acetic ester as well as preparation method and application thereof |
| CN105579461A (en) * | 2013-09-26 | 2016-05-11 | 旭化成化学株式会社 | Alkyl tin compound |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2589163B2 (en) * | 1988-09-28 | 1997-03-12 | 日東化成株式会社 | Preparation of asymmetric triorganotin halides. |
| US5145976A (en) * | 1989-10-20 | 1992-09-08 | Air Products And Chemicals, Inc. | Polymeric diorganotin catalysts for use in polyurethane systems |
| EP0472783A1 (en) * | 1990-08-28 | 1992-03-04 | Pharmachemie B.V. | Anti-tumor compositions and compounds |
| EP2662379A1 (en) | 2012-05-07 | 2013-11-13 | Universiteit Antwerpen | Recycling of organotin compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL203480A (en) * | 1953-07-03 | 1900-01-01 | ||
| US3043858A (en) * | 1958-08-28 | 1962-07-10 | Dow Corning | Silalkyltin compounds |
| FR1253725A (en) * | 1960-04-08 | 1961-02-10 | Hoechst Ag | Pesticides based on organic tin compounds |
| FR1288441A (en) * | 1961-04-25 | 1962-03-24 | Ici Ltd | Manufacture of covalent inorganic isocyanates and their derivatives |
| GB1163738A (en) * | 1965-10-27 | 1969-09-10 | Pfizer & Co C | Process for Suppressing the Growth of Microorganisms |
| US3448131A (en) * | 1966-03-30 | 1969-06-03 | Union Carbide Corp | Process for preparing trihydrocarbyltin acetoacetates |
| FR1541011A (en) * | 1966-07-28 | 1968-10-04 | Ciba Geigy | New pesticide agents |
| FR1499737A (en) * | 1966-08-11 | 1967-10-27 | United States Borax Chem | Organotin compounds, their preparation and applications |
| US3471539A (en) * | 1967-08-23 | 1969-10-07 | Nitto Kasei Co Ltd | Method for preparing triorganotin halides and bis(triorganotin) oxides |
| US3475472A (en) * | 1967-09-21 | 1969-10-28 | Nitto Kasei Co Ltd | Method for preparing triorganotin halides and bis(triorganotin) oxides |
| US3476472A (en) * | 1968-02-26 | 1969-11-04 | Eastman Kodak Co | Strip retrieval device |
| US3677738A (en) * | 1968-02-28 | 1972-07-18 | Tenneco Chem | Method for the control of pests with triorganotin (substituted phenoxides) |
| US3789057A (en) * | 1968-11-04 | 1974-01-29 | M & T Chemicals Inc | A process for preparing symetrical triorganotin halides |
| DE1958639A1 (en) * | 1968-11-22 | 1970-06-18 | Norio Saito | New organic tin compounds, their production and use |
| US3634479A (en) * | 1970-09-08 | 1972-01-11 | Dow Chemical Co | Tin-oxygen-phosphorous bond compounds |
| CH524312A (en) * | 1970-11-18 | 1972-06-30 | Bayer Ag | Compsns contng tri-substd tin azolides |
| US3657451A (en) * | 1971-02-08 | 1972-04-18 | Shell Oil Co | Organo-tin miticides and method of using the same |
| US3988449A (en) * | 1971-08-28 | 1976-10-26 | Bayer Aktiengesellschaft | Trisalkyl tin 1,2,4-triazole insecticidal and acaricidal agents |
| GB1353540A (en) * | 1971-12-08 | 1974-05-22 | Ici Ltd | Organo-metallic compounds |
| US3892863A (en) * | 1972-10-05 | 1975-07-01 | M & T Chemicals Inc | Fungicidal and miticidal method containing triorganotin compounds |
| JPS526257B2 (en) * | 1972-11-29 | 1977-02-21 | ||
| US3923998A (en) * | 1972-12-04 | 1975-12-02 | M & T Chemicals Inc | Certain triorganotin compounds used to combat plant fungi |
| NO139149C (en) * | 1972-12-04 | 1979-01-31 | M & T Chemicals Inc | AGENT FOR FIGHTING MUSHROOMS AND CENTERS |
| US4343815A (en) * | 1973-08-30 | 1982-08-10 | M&T Chemicals Inc. | Method for combating fungi and mites using certain triorganotin compounds |
| US3906103A (en) * | 1974-03-14 | 1975-09-16 | M & T Chemicals Inc | Pesticidal composition and method |
| US4010276A (en) * | 1974-07-10 | 1977-03-01 | M & T Chemicals Inc. | Certain triorganotin compounds used to combat mites |
| US4058545A (en) * | 1976-08-03 | 1977-11-15 | M&T Chemicals Inc. | Method for preparing tri(β-substituted phenethyl)tin halides |
| GB1581269A (en) * | 1976-08-17 | 1980-12-10 | M & T Chemicals Inc | Tricyclopentyltin compounds and pesticidal compositions containing same |
| GB1579410A (en) * | 1977-03-03 | 1980-11-19 | M & T Chemicals Inc | Triorganotin compounds and method for combating insects using same |
| GB1602160A (en) * | 1978-04-26 | 1981-11-11 | Negretti & Zambra Aviat Ltd | Pyrometers |
| US4324798A (en) * | 1980-10-08 | 1982-04-13 | M&T Chemicals Inc. | Fungicidal bis(substituted phenyl)alkyltin compounds |
| GB2113093B (en) * | 1982-01-19 | 1985-01-03 | Dow Chemical Co | Improvements in pesticidal formulations |
| JPS6172793A (en) * | 1984-09-18 | 1986-04-14 | Kyodo Yakuhin Kk | Tris(2,2-dimethylphenethyl)tin carboxylic acid ester and itos preparation and acaridide containing the mase |
-
1985
- 1985-09-03 AR AR85305136A patent/AR243195A1/en active
-
1986
- 1986-08-21 US US06/898,688 patent/US4774235A/en not_active Expired - Fee Related
- 1986-08-26 CA CA000516822A patent/CA1283417C/en not_active Expired - Fee Related
- 1986-08-26 ZA ZA866451A patent/ZA866451B/en unknown
- 1986-09-02 ES ES8601570A patent/ES2001413A6/en not_active Expired
- 1986-09-02 JP JP61206974A patent/JPS62149689A/en active Granted
- 1986-09-02 BR BR8604209A patent/BR8604209A/en not_active IP Right Cessation
- 1986-09-03 DE DE8686306832T patent/DE3683815D1/en not_active Expired - Fee Related
- 1986-09-03 CN CN86106818A patent/CN1016132B/en not_active Expired
- 1986-09-03 EP EP86306832A patent/EP0214842B1/en not_active Expired - Lifetime
- 1986-09-03 KR KR1019860007370A patent/KR920002887B1/en not_active IP Right Cessation
- 1986-09-03 GB GB8621231A patent/GB2179943B/en not_active Expired
-
1988
- 1988-05-06 US US07/191,058 patent/US4935408A/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105579461A (en) * | 2013-09-26 | 2016-05-11 | 旭化成化学株式会社 | Alkyl tin compound |
| CN105579461B (en) * | 2013-09-26 | 2020-02-14 | 旭化成株式会社 | Alkyl tin compound |
| CN104804035A (en) * | 2015-04-15 | 2015-07-29 | 衡阳师范学院 | Tricyclohexanyl-tin 2,7-naphthyl dioxy acetic ester as well as preparation method and application thereof |
| CN104804035B (en) * | 2015-04-15 | 2017-09-29 | 衡阳师范学院 | A kind of naphthalene dioxy acetic acid esters of Tricyclohexyltin 2,7 and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2001413A6 (en) | 1988-05-16 |
| CN1016132B (en) | 1992-04-08 |
| AR243195A1 (en) | 1993-07-30 |
| US4774235A (en) | 1988-09-27 |
| BR8604209A (en) | 1987-04-28 |
| US4935408A (en) | 1990-06-19 |
| EP0214842A2 (en) | 1987-03-18 |
| EP0214842A3 (en) | 1989-11-29 |
| ZA866451B (en) | 1987-05-27 |
| EP0214842B1 (en) | 1992-02-05 |
| CA1283417C (en) | 1991-04-23 |
| JPH0353319B2 (en) | 1991-08-14 |
| GB2179943A (en) | 1987-03-18 |
| DE3683815D1 (en) | 1992-03-19 |
| KR920002887B1 (en) | 1992-04-06 |
| AU589206B2 (en) | 1989-10-05 |
| KR870003125A (en) | 1987-04-15 |
| GB8621231D0 (en) | 1986-10-08 |
| GB2179943B (en) | 1989-08-16 |
| JPS62149689A (en) | 1987-07-03 |
| AU6185786A (en) | 1987-03-05 |
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| C13 | Decision | ||
| C14 | Grant of patent or utility model | ||
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Free format text: CORRECT: PATENTEE; FROM: N.V. PHILIPS OPTICAL LAMP MANUFACTURING COMPANY TO: N.V. PHILIPS OPTICALLAMP LTD., CO. |
|
| CP01 | Change in the name or title of a patent holder |
Patentee after: Philips Electronics N. V. Patentee before: N.V. Philips' Gloeipenfabrieken |